JP2009013482A - Nickel powder or nickel alloy powder, and production method therefor - Google Patents
Nickel powder or nickel alloy powder, and production method therefor Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 150000002815 nickel Chemical class 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000011164 primary particle Substances 0.000 claims abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 150000003839 salts Chemical group 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000012266 salt solution Substances 0.000 abstract description 7
- -1 boron hydride compound Chemical class 0.000 abstract description 4
- 229910010277 boron hydride Inorganic materials 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008213 purified water Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000004687 hexahydrates Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000006072 paste Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Powder Metallurgy (AREA)
- Non-Insulated Conductors (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
本発明は、平均一次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル粉又はニッケル合金粉とその製造方法に関するものである。 The present invention relates to nickel powder or nickel alloy powder in which particles having an average primary particle diameter of 50 nm to 1 μm are three-dimensionally connected and a method for producing the same.
導電性を有するニッケル等の微粉末は、混練性やペースト性状が優秀で、また薄層化が可能であることから、導電性フィラーとして、塗料、樹脂、ゴム、ペースト、接着剤やインクなど幅広い用途に使用されている。 Conductive nickel and other fine powders are excellent in kneading and pasting properties and can be made into thin layers. Therefore, a wide range of conductive fillers such as paints, resins, rubbers, pastes, adhesives and inks can be used. Used for applications.
ニッケル粉の製造方法の物理的方法として、金属を機械的に粉砕する方法、溶融金属を噴霧冷却するアトマイズ法などがあるが、いずれも微粉末を得るのは難しい。金属を加熱蒸発させ、金属蒸気を凝集させ、金属微粉末を合成するアーク放電法などもあるが、設備が高価で生産性が低いという問題点があった。 As a physical method for producing nickel powder, there are a method of mechanically pulverizing a metal, an atomizing method of spraying and cooling molten metal, and it is difficult to obtain a fine powder. There is an arc discharge method in which metal is heated and evaporated, metal vapor is aggregated, and fine metal powder is synthesized. However, there is a problem that equipment is expensive and productivity is low.
化学的方法としては、加熱揮発させた金属塩を還元する気相法があるが、これも設備が高価で生産性が低いという問題点があった。また、塩基性炭酸ニッケルや水酸化ニッケルを還元剤により還元する液相法（特許文献１及び特許文献２）では、これら難溶性のニッケル塩を還元する場合、還元反応に要する時間が長くなるという問題があった。 As a chemical method, there is a gas phase method in which a metal salt which is volatilized by heating is reduced. However, this also has a problem that the equipment is expensive and the productivity is low. Moreover, in the liquid phase method (patent documents 1 and 2) which reduces basic nickel carbonate and nickel hydroxide with a reducing agent, when these poorly soluble nickel salts are reduced, the time required for the reduction reaction is increased. There was a problem.
また、物理的方法、化学的方法である気相法、液相法では、ナノ粒子が三次元的に連結したニッケル系金属粉の合成は困難であった。 Further, in the vapor phase method and the liquid phase method, which are physical methods and chemical methods, it is difficult to synthesize nickel-based metal powders in which nanoparticles are three-dimensionally connected.
一方、金属塩の水溶液に還元剤を添加して還元する湿式還元法では、ニッケル粉は、通常、球状、楕円形、あるいは、フレーク状をしており、多量に添加しないと上記材料に安定した導電性を付与することができなかった。 On the other hand, in the wet reduction method in which a reducing agent is added to an aqueous solution of a metal salt for reduction, the nickel powder is usually spherical, elliptical, or flaky, and stable to the above materials unless added in a large amount. Electrical conductivity could not be imparted.
多量の添加は、ニッケル粉によるコストアップだけでなく、上記材料例えば樹脂やゴムの性能を著しく低下させたり、接着性を低下させたり、塗膜にクラックを生じさせるなど副作用的弊害が大きい。 Addition of a large amount not only raises the cost due to nickel powder, but also has serious side effects such as significantly reducing the performance of the above-mentioned materials such as resin and rubber, lowering the adhesion, and causing cracks in the coating film.
これら問題点を解決するために、特許文献３では、連鎖状の金属粉が提案されている。特許文献４では、ニッケルとアルミニウムの合金から製造するスポンジニッケルが提案されている。
しかしながら、連鎖状のニッケル粉の製造には、３価チタンイオン、４価チタンイオンなど特殊な還元剤が必要で、また前記チタンイオンの錯化剤が必要となる場合もある。また、スポンジニッケルの製造では、ニッケルとアルミニウムの合金から合金粉末を作製し、３００度Ｃから８００度Ｃの温度に保持して均質化し、次いで、合金粉末をアルカリ水溶液に投入して、アルミニウムを溶出させるという多数の工程からなり、決して簡単な製造方法ではない。 However, the production of the chain-like nickel powder requires a special reducing agent such as trivalent titanium ion or tetravalent titanium ion, and may require a complexing agent of the titanium ion. In the manufacture of sponge nickel, an alloy powder is prepared from an alloy of nickel and aluminum, is kept at a temperature of 300 ° C. to 800 ° C. and homogenized, and then the alloy powder is put into an alkaline aqueous solution to obtain aluminum. It consists of a number of steps of elution and is not a simple manufacturing method.
本発明の目的は、簡単な製造方法によって製造できる、平均一次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル粉又はニッケル合金粉の金属粉とその製造方法を提供することにある。 An object of the present invention is to provide a metal powder of nickel powder or nickel alloy powder in which particles having an average primary particle size of 50 nm or more and 1 μm or less can be three-dimensionally connected and can be manufactured by a simple manufacturing method, and a manufacturing method thereof. is there.
本発明は、少なくともニッケル塩を含む水溶液と、少なくとも水素化ホウ素化合物を含む還元剤水溶液を反応させる還元反応工程と、生成した沈殿物を分離する沈殿分離工程と、分離した沈殿物を減圧下で加熱する減圧加熱工程を備える、平均一次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル粉又はニッケル合金粉とその製造方法に関するものである。 The present invention includes a reduction reaction step of reacting an aqueous solution containing at least a nickel salt with an aqueous reducing agent solution containing at least a borohydride compound, a precipitation separation step of separating the produced precipitate, and the separated precipitate under reduced pressure. The present invention relates to a nickel powder or nickel alloy powder in which particles having an average primary particle diameter of 50 nm or more and 1 μm or less are connected three-dimensionally, and a method for producing the same.
本発明の減圧加熱工程における減圧度は、５×１０４Ｐａ以下であり、かつ加熱温度は、７０度Ｃ以上１，０００度Ｃ以下である。 The degree of reduced pressure in the reduced pressure heating step of the present invention is 5 × 10 4 Pa or less, and the heating temperature is 70 ° C. or more and 1,000 ° C. or less.
本発明の、平均一次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル粉又はニッケル合金粉の製造方法は、プロセスが簡単で、かつ、ニッケル塩が効率よく還元されるため、収率が高く経済的である。また、本発明のニッケル粉又はニッケル合金粉は、ナノ粒子が三次元的に連結しているため、例えば、導電性フィラーとして、塗料、樹脂、ゴム、ペースト、接着剤やインクなど幅広い用途に使用することができる。また、本発明のニッケル系金属粉は、スポンジ状ニッケル触媒としても期待できる。 The method for producing nickel powder or nickel alloy powder in which particles having an average primary particle diameter of 50 nm or more and 1 μm or less are three-dimensionally connected according to the present invention is simple in process and the nickel salt is efficiently reduced. High yield and economical. In addition, the nickel powder or nickel alloy powder of the present invention is used in a wide range of applications such as paint, resin, rubber, paste, adhesive and ink as the conductive filler because the nanoparticles are three-dimensionally connected. can do. The nickel-based metal powder of the present invention can also be expected as a sponge nickel catalyst.
本発明の製造方法は、少なくともニッケル塩を含むニッケル塩水溶液と、少なくとも水素化ホウ素化合物を含む水溶液である還元剤水溶液を反応させる工程により、ニッケル及びホウ素を含む沈殿物を生成させ、この沈殿物を分離及び洗浄工程を経た後、５×１０４Ｐａ以下の減圧下で７０度Ｃ以上１，０００度Ｃ以下の温度で加熱する工程により、一次粒子径が５０ｎｍ以上１μｍ以下の粒子が融着して三次元的に連結した構造を有するニッケル粉又はニッケル合金粉の製造方法である。 In the production method of the present invention, a nickel salt aqueous solution containing at least a nickel salt and a reducing agent aqueous solution that is an aqueous solution containing at least a borohydride compound are reacted to generate a precipitate containing nickel and boron. After the separation and washing step, particles having a primary particle size of 50 nm or more and 1 μm or less are fused by heating at a temperature of 70 ° C. or more and 1,000 ° C. or less under a reduced pressure of 5 × 10 4 Pa or less. And a method for producing nickel powder or nickel alloy powder having a three-dimensionally connected structure.
本発明において、ニッケル塩とは、水に溶解しニッケルイオンを生成するニッケル化合物のことを指す。例えば、硫酸ニッケル、塩化ニッケル、硝酸ニッケル、酢酸ニッケル、アミド硫酸ニッケルなどが挙げられる。また、これらニッケル塩の２種以上のものを混合して用いてもよい。 In the present invention, the nickel salt refers to a nickel compound that dissolves in water and generates nickel ions. For example, nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, nickel amide sulfate and the like can be mentioned. Two or more of these nickel salts may be mixed and used.
ニッケルとともに還元されるニッケル以外の元素を含む化合物を添加してもよい。例えば、添加しうる元素としてはＣｏ、Ｆｅ、Ｗ、Ｃｒ、Ｍｎ、Ｖ、Ｃｕ、Ｚｎ、Ｍｏ、Ｐｄ、Ｓｎ、Ｒｅ、Ｐ等ニッケルとともに還元される元素の化合物であればよい。添加量はとくに限定されないが、元素比で５０％以下であればよい。過剰に添加すると三次元的に連結した構造が得られないことがある。 You may add the compound containing elements other than nickel reduced with nickel. For example, the elements that can be added may be compounds of elements that are reduced together with nickel, such as Co, Fe, W, Cr, Mn, V, Cu, Zn, Mo, Pd, Sn, Re, and P. The addition amount is not particularly limited, but may be 50% or less in terms of element ratio. If added excessively, a three-dimensionally connected structure may not be obtained.
本発明において、水素化ホウ素化合物は、還元効率を上げるために、水素化ホウ素ナトリウム、水素化ホウ素カリウムからなる群から選ばれる少なくとも１つであることが好ましい。水素化ホウ素化合物の使用量は、ニッケルイオン１ｍｏｌに対して０．２ｍｏｌ以上５ｍｏｌ以下であることが、還元効率の点でより好ましい。５ｍｏｌよりも多く使用しても差し支えないが、経済的でない。 In the present invention, the borohydride compound is preferably at least one selected from the group consisting of sodium borohydride and potassium borohydride in order to increase the reduction efficiency. The amount of the borohydride compound used is more preferably 0.2 mol or more and 5 mol or less with respect to 1 mol of nickel ions from the viewpoint of reduction efficiency. Although it is possible to use more than 5 mol, it is not economical.
本発明において、錯化剤は、収率を向上させるために、ニッケル塩を含む水溶液、水素化ホウ素化合物を含む還元剤水溶液の少なくとも一方に添加することが好ましい。錯化剤は、ニッケルイオンと錯体を形成するもので、酢酸、マロン酸、酒石酸、クエン酸、りんご酸、乳酸、プロピオン酸、ギ酸、酪酸、アクリル酸、ポリアクリル酸等のカルボン酸、もしくはその塩、アンモニア、塩化アンモニウム、硫酸アンモニウム等のアンモニウム塩、エチレンジアミン、ＥＤＴＡ等のアミン化合物、ヘキサメタリン酸、ピロリン酸等のリン酸塩化合物、グリシン、グルタミン酸等のアミノ酸、チオグリコール酸等のチオール化合物等が挙げられ、２種以上同時に用いてもよい。これらの化合物はｐＨ調整剤、緩衝剤としても作用するため好ましい。 In the present invention, the complexing agent is preferably added to at least one of an aqueous solution containing a nickel salt and an aqueous reducing agent solution containing a borohydride compound in order to improve the yield. The complexing agent forms a complex with nickel ions, and is a carboxylic acid such as acetic acid, malonic acid, tartaric acid, citric acid, malic acid, lactic acid, propionic acid, formic acid, butyric acid, acrylic acid, polyacrylic acid, or the like. Salts, ammonium salts such as ammonia, ammonium chloride and ammonium sulfate, amine compounds such as ethylenediamine and EDTA, phosphate compounds such as hexametaphosphoric acid and pyrophosphoric acid, amino acids such as glycine and glutamic acid, and thiol compounds such as thioglycolic acid Two or more of them may be used simultaneously. These compounds are preferable because they also act as pH adjusters and buffers.
さらにニッケル塩水溶液、または還元剤水溶液、またはその双方にｐＨ調整、及び緩衝作用を目的として、ホウ酸、リン酸、炭酸、塩酸、硫酸、フッ酸、硝酸、酢酸並びにそれらの塩類等を添加することもできる。 Furthermore, boric acid, phosphoric acid, carbonic acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid, acetic acid and salts thereof are added to the aqueous nickel salt solution, the reducing agent aqueous solution, or both for the purpose of pH adjustment and buffer action. You can also.
またニッケル塩水溶液、または還元剤水溶液、またはその双方に界面活性剤など添加することもできる。 A surfactant or the like can also be added to the nickel salt aqueous solution, the reducing agent aqueous solution, or both.
また還元剤水溶液は、還元剤の自己分解を防ぐために、水酸化ナトリウム、水酸化カリウム、アンモニア水等の塩基性化合物を添加し、ｐＨを７以上にすることが好ましい。 The aqueous reducing agent solution preferably has a pH of 7 or more by adding a basic compound such as sodium hydroxide, potassium hydroxide, or aqueous ammonia in order to prevent the reducing agent from self-decomposing.
本発明において、ニッケル塩水溶液と還元剤水溶液との反応方法は、とくに限定されるものではないが、後述する反応温度の制御しやすさ、還元反応の制御しやすさという点で、ニッケル塩水溶液に還元剤水溶液を１００ｍＬ／分以下の速度で滴下する方法が好ましい。 In the present invention, the reaction method of the nickel salt aqueous solution and the reducing agent aqueous solution is not particularly limited. However, the nickel salt aqueous solution is easy to control the reaction temperature described later and the control of the reduction reaction. A method of dropping the aqueous reducing agent solution at a rate of 100 mL / min or less is preferred.
本発明において、反応温度は特に限定されず、好ましくは水溶液の融点以上沸点以下、より好ましくは５０度Ｃ以上であることが収率の向上のために好ましい。 In the present invention, the reaction temperature is not particularly limited, and is preferably from the melting point to the boiling point of the aqueous solution, more preferably from 50 ° C. to improve the yield.
反応溶液からの沈殿物の分離方法は、ろ過、デカンテーョン、遠心分離、磁気選鉱等、特に限定されない。沈殿物は精製水による１回以上の洗浄を行うことが好ましい。 The method for separating the precipitate from the reaction solution is not particularly limited, such as filtration, decantation, centrifugation, and magnetic beneficiation. The precipitate is preferably washed once or more with purified water.
反応液から分離・洗浄した沈殿物は、乾燥させないまま減圧加熱する。好ましくは、ろ過した沈殿物を減圧加熱炉に投入し、５×１０４ＭＰａ未満の減圧下で７０度Ｃ以上１，０００度Ｃ未満の温度で加熱する。この範囲であると、平均一次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結した構造のニッケル粉又はニッケル合金粉が得られる。 The precipitate separated and washed from the reaction solution is heated under reduced pressure without being dried. Preferably, the filtered precipitate is put into a reduced pressure heating furnace and heated at a temperature of 70 ° C. or more and less than 1,000 ° C. under a reduced pressure of less than 5 × 10 4 MPa. Within this range, nickel powder or nickel alloy powder having a structure in which particles having an average primary particle diameter of 50 nm to 1 μm are three-dimensionally connected can be obtained.
本発明の製造方法で作製されたニッケル粉又はニッケル合金粉は、ニッケルの含有量が、７５重量％以上であり、ホウ素の含有量が、０．１重量％以上２０重量％以下である。 The nickel powder or nickel alloy powder produced by the production method of the present invention has a nickel content of 75% by weight or more and a boron content of 0.1% by weight or more and 20% by weight or less.
以下、実施例によって、本発明を詳細に説明する。各実施例及び比較例で作製したニッケル粉又はニッケル合金粉の諸物性は、下記の方法で測定した。
（１）走査型電子顕微鏡（ＳＥＭ）観察
日立サイエンスシステムズ製の低真空型電子顕微鏡“ＳＥＭＥＤＸ３ＴＴｙｐｅＮ”を用いた。
（２）ホウ素含有量
島津製作所製の高周波プラズマ発光分析装置“ＩＣＰＳ−８０００”を用いた。
（３）元素分析
日立サイエンスシステムズ製の低真空型電子顕微鏡“ＳＥＭＥＤＸ３ＴＴｙｐｅＮ”を用いた。
Hereinafter, the present invention will be described in detail by way of examples. Various physical properties of the nickel powder or nickel alloy powder produced in each example and comparative example were measured by the following methods.
(1) Observation with Scanning Electron Microscope (SEM) A low-vacuum electron microscope “SEMEDX3TTypeN” manufactured by Hitachi Science Systems was used.
(2) Boron content A high frequency plasma emission analyzer “ICPS-8000” manufactured by Shimadzu Corporation was used.
(3) Elemental analysis A low-vacuum electron microscope “SEMEDX3TTypeN” manufactured by Hitachi Science Systems was used.
水素化ホウ素ナトリウム０．３８ｇ及び水酸化ナトリウム１．００ｇを精製水に溶解して１００ｍＬとし、還元剤水溶液とした。該還元剤水溶液のｐＨは１２であった。次に、硫酸ニッケル（２）六水和物２．６３ｇ及び酒石酸カリウムナトリウム四水和物（ロッシェル塩）１．４１ｇを精製水に溶解して１００ｍＬとし、ニッケル塩水溶液を得た。この水溶液を７５度Ｃに加熱して攪拌した。
７５度Ｃに保ち攪拌しているニッケル塩水溶液に、還元剤水溶液を１０分かけて滴下したところ黒色の沈殿が生じた。さらに７５度Ｃを保ち１時間攪拌した後、上澄み液をデカンテーションによって取り除いた後、精製水１００ｍＬを加えて超音波を当てて洗浄した。次いで吸引ろ過により沈殿を分離し、さらに精製水１００ｍＬを用いて洗浄、吸引して黒色の粉末を得た。この粉末を乾燥させないまま、２×１０３Ｐａ未満の減圧下１５０度Ｃで２時間加熱したところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．６７ｇが得られた。該ニッケル合金粉のＳＥＭ写真を図１に示す。ＩＣＰ発光分析の結果、該ニッケル合金粉のホウ素含有量は４．６重量パーセントであった。
0.38 g of sodium borohydride and 1.00 g of sodium hydroxide were dissolved in purified water to make 100 mL, and a reducing agent aqueous solution was prepared. The pH of the reducing agent aqueous solution was 12. Next, 2.63 g of nickel sulfate (2) hexahydrate and 1.41 g of potassium sodium tartrate tetrahydrate (Rochelle salt) were dissolved in purified water to 100 mL to obtain an aqueous nickel salt solution. This aqueous solution was heated to 75 ° C. and stirred.
When the reducing agent aqueous solution was added dropwise to the stirring nickel salt aqueous solution at 75 ° C. over 10 minutes, a black precipitate was formed. After further stirring at 75 ° C. for 1 hour, the supernatant was removed by decantation, and 100 mL of purified water was added and washed by applying ultrasonic waves. Next, the precipitate was separated by suction filtration, further washed with 100 mL of purified water, and sucked to obtain a black powder. When this powder is heated for 2 hours at 150 ° C. under reduced pressure of less than 2 × 10 3 Pa without drying, a nickel alloy powder in which particles having a gray average primary particle size of 50 nm to 1 μm are three-dimensionally connected. 0.67 g was obtained. An SEM photograph of the nickel alloy powder is shown in FIG. As a result of ICP emission analysis, the boron content of the nickel alloy powder was 4.6 weight percent.
水素化ホウ素ナトリウム０．３８ｇを精製水に溶解して１００ｍＬとし、還元剤水溶液とした。該還元剤水溶液のｐＨは１０であった。次に、硫酸ニッケル（２）六水和物２．６３ｇを精製水に溶解して１００ｍＬとし、ニッケル塩水溶液を得た。この水溶液を室温（２３度Ｃ）で攪拌した。
室温で攪拌しているニッケル塩水溶液に、還元剤水溶液を１０分かけて滴下したところ黒色の沈殿が生じた。さらに１時間攪拌した後、上澄み液をデカンテーションによって取り除いた後、精製水１００ｍＬ加えて超音波を当てて洗浄した。次いで吸引ろ過により沈殿を分離し、さらに精製水１００ｍＬを用いて洗浄、吸引して黒色の粉末を得た。この粉末を乾燥させないまま、２×１０３Ｐａ未満の減圧下１５０度Ｃで２時間加熱したところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．３４ｇが得られた。該ニッケル合金粉のホウ素含有量は３．４重量パーセントであった。
Sodium borohydride (0.38 g) was dissolved in purified water to make 100 mL, and a reducing agent aqueous solution was prepared. The pH of the reducing agent aqueous solution was 10. Next, 2.63 g of nickel sulfate (2) hexahydrate was dissolved in purified water to 100 mL to obtain an aqueous nickel salt solution. The aqueous solution was stirred at room temperature (23 degrees C).
When a reducing agent aqueous solution was dropped into a nickel salt aqueous solution stirred at room temperature over 10 minutes, a black precipitate was formed. After further stirring for 1 hour, the supernatant was removed by decantation, and then 100 mL of purified water was added and washed by applying ultrasonic waves. Next, the precipitate was separated by suction filtration, further washed with 100 mL of purified water, and sucked to obtain a black powder. When this powder is heated for 2 hours at 150 ° C. under reduced pressure of less than 2 × 10 3 Pa without drying, a nickel alloy powder in which particles having a gray average primary particle size of 50 nm to 1 μm are three-dimensionally connected. 0.34 g was obtained. The boron content of the nickel alloy powder was 3.4 weight percent.
還元剤水溶液を２２秒で滴下した以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．４５ｇが得られた。該ニッケル合金粉のホウ素含有量は４．２重量パーセントであった。 When the same operation as in Example 1 was performed except that the reducing agent aqueous solution was dropped in 22 seconds, 0.45 g of nickel alloy powder in which particles having a gray average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected. was gotten. The boron content of the nickel alloy powder was 4.2 weight percent.
還元剤水溶液として、水素化ホウ素ナトリウム０．３８ｇ及び水酸化ナトリウム２．００ｇを精製水に溶解して１００ｍＬとしたもの（ｐＨ１２）を用い、ニッケル塩水溶液として、硫酸ニッケル（２）六水和物５．２６ｇ及び酒石酸カリウムナトリウム四水和物１．４１ｇを精製水に溶解して１００ｍＬとしたものを用いた以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉１．２７ｇが得られた。該ニッケル合金粉のホウ素含有量は１．８重量パーセントであった。 As an aqueous reducing agent solution, 0.38 g of sodium borohydride and 2.00 g of sodium hydroxide were dissolved in purified water to make 100 mL (pH 12), and nickel sulfate (2) hexahydrate was used as the nickel salt aqueous solution. When the same operation as in Example 1 was performed except that 5.26 g and 1.41 g of potassium sodium tartrate tetrahydrate were dissolved in purified water to make 100 mL, the gray average primary particle diameter was As a result, 1.27 g of nickel alloy powder in which particles of 50 nm to 1 μm were three-dimensionally connected was obtained. The boron content of the nickel alloy powder was 1.8 weight percent.
ニッケル塩水溶液として、硫酸ニッケル（２）六水和物２．６３ｇ及びグリシン０．３８ｇを精製水に溶解して１００ｍＬとしたものを用いた以外、実施例１と同様の操作を行なったところ灰色の、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．６７ｇが得られた。該ニッケル合金粉のＳＥＭ写真を図２に示す。該ニッケル合金粉のホウ素含有量は３．６重量パーセントであった。 When the same operation as in Example 1 was performed except that 2.63 g of nickel sulfate (2) hexahydrate and 0.38 g of glycine were dissolved in purified water to make 100 mL as an aqueous nickel salt solution, gray was obtained. Thus, 0.67 g of nickel alloy powder in which particles having a gray average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected was obtained. An SEM photograph of the nickel alloy powder is shown in FIG. The boron content of the nickel alloy powder was 3.6 weight percent.
ニッケル塩水溶液として、硫酸ニッケル（２）六水和物２．６３ｇ及びエチレンジアミン０．３０ｇを精製水に溶解して１００ｍＬとしたものを用いた以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．６９ｇが得られた。該ニッケル合金粉のホウ素含有量は２．８重量パーセントであった。 When the same operation as in Example 1 was performed, except that 2.63 g of nickel sulfate (2) hexahydrate and 0.30 g of ethylenediamine were dissolved in purified water to make 100 mL as an aqueous nickel salt solution, As a result, 0.69 g of nickel alloy powder in which gray particles having an average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected was obtained. The boron content of the nickel alloy powder was 2.8 weight percent.
ニッケル塩水溶液として、硫酸ニッケル（２）六水和物２．６３ｇ及び硫酸アンモニウム０．６６ｇを精製水に溶解して１００ｍＬとしたもの（ｐＨ１２）を用いた以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．６８ｇが得られた。該ニッケル合金粉のホウ素含有量は２．５重量パーセントであった。 The same operation as in Example 1 was performed except that 2.63 g of nickel sulfate (2) hexahydrate and 0.66 g of ammonium sulfate were dissolved in purified water to make 100 mL (pH 12). As a result, 0.68 g of nickel alloy powder in which particles having a gray average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected was obtained. The boron content of the nickel alloy powder was 2.5 weight percent.
ニッケル塩水溶液として、アミド硫酸ニッケル（２）四水和物３．２３ｇ及び酒石酸カリウムナトリウム四水和物１．４１ｇを精製水に溶解して１００ｍＬとしたものを用いた以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．６６ｇが得られた。該ニッケル合金粉のホウ素含有量は１．２重量パーセントであった。 The same as in Example 1, except that the aqueous solution of nickel salt was prepared by dissolving 3.23 g of nickel amidosulfate (2) tetrahydrate and 1.41 g of potassium sodium tartrate tetrahydrate in purified water to make 100 mL. As a result, 0.66 g of nickel alloy powder in which particles having a gray average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected was obtained. The boron content of the nickel alloy powder was 1.2 weight percent.
還元剤水溶液として、水素化ホウ素カリウム０．５４ｇ及び水酸化ナトリウム１．００ｇを精製水に溶解して１００ｍＬとしたもの（ｐＨ１２．５）を用いた以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．７０ｇが得られた。該ニッケル合金粉のホウ素含有量は１．０重量パーセントであった。 The same operation as in Example 1 was performed except that 0.54 g of potassium borohydride and 1.00 g of sodium hydroxide were dissolved in purified water to make 100 mL (pH 12.5) as the reducing agent aqueous solution. As a result, 0.70 g of nickel alloy powder in which particles having a gray average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected was obtained. The boron content of the nickel alloy powder was 1.0 weight percent.
ニッケル塩水溶液の代わりに、硫酸ニッケル（２）六水和物２．３７ｇ及び硫酸コバルト（２）七水和物０．２８ｇ及び酒石酸カリウムナトリウム四水和物１．４１ｇを精製水に溶解して１００ｍＬとしたニッケル−コバルト塩水溶液を用いた以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．７４ｇが得られた。元素分析の結果、ニッケルとコバルトの元素比率は９：１であった。該ニッケル合金粉のホウ素含有量は４．０重量パーセントであった。 Instead of aqueous nickel salt solution, 2.37 g of nickel sulfate (2) hexahydrate, 0.28 g of cobalt sulfate (2) heptahydrate and 1.41 g of potassium sodium tartrate tetrahydrate were dissolved in purified water. Except for using 100 mL of nickel-cobalt salt aqueous solution, the same operation as in Example 1 was performed. As a result, nickel alloy powder in which gray particles having an average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected 0 .74 g was obtained. As a result of elemental analysis, the elemental ratio of nickel and cobalt was 9: 1. The boron content of the nickel alloy powder was 4.0 weight percent.
減圧加熱の減圧度を２×１０４Ｐａとした以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．７２ｇが得られた。該ニッケル合金粉のホウ素含有量は４．７重量パーセントであった。 A nickel alloy in which gray particles having an average primary particle diameter of 50 nm or more and 1 μm or less are three-dimensionally connected except that the degree of reduced pressure of the reduced pressure heating is 2 × 10 4 Pa. 0.72 g of powder was obtained. The boron content of the nickel alloy powder was 4.7 weight percent.
減圧加熱の温度を１００度Ｃとした以外、実施例１と同様の操作を行なったところ、灰色の平均１次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル合金粉０．６８ｇが得られた。該ニッケル合金粉のホウ素含有量は４．５重量パーセントであった。 Except that the temperature of the reduced pressure heating was set to 100 ° C., the same operation as in Example 1 was performed. As a result, a nickel alloy powder in which particles having a gray average primary particle diameter of 50 nm to 1 μm were three-dimensionally connected was obtained. 68 g was obtained. The boron content of the nickel alloy powder was 4.5 weight percent.
（比較例１）
実施例１において、減圧加熱の温度を５０度Ｃとした以外、実施例１と同様の操作を行なったが、黒色の粉末が得られた。該粉末をＳＥＭで観察した結果、５０ｎｍ以下の粒子の凝集物であった。
(Comparative Example 1)
In Example 1, the same operation as in Example 1 was performed except that the temperature of the reduced pressure heating was set to 50 ° C., but a black powder was obtained. As a result of observing the powder by SEM, it was an aggregate of particles of 50 nm or less.
（比較例２）
実施例１において、減圧せず大気圧下１５０度Ｃで２時間加熱した以外、実施例１と同様の操作を行なったが黒色の粉末が得られた。該粉末をＳＥＭで観察した結果、５０ｎｍ以下の粒子の凝集物であった。
(Comparative Example 2)
In Example 1, the same operation as in Example 1 was carried out except that heating was performed at 150 ° C. under atmospheric pressure for 2 hours without reducing pressure, but a black powder was obtained. As a result of observing the powder by SEM, it was an aggregate of particles of 50 nm or less.
本発明の、平均一次粒子径が５０ｎｍ以上１μｍ以下の粒子が三次元的に連結したニッケル粉又はニッケル合金粉の製造方法は、プロセスが簡単で、かつ、ニッケル塩が効率よく還元されるため、収率が高く経済的である。また、本発明のニッケル粉又はニッケル合金粉は、ナノ粒子が三次元的に連結しているため、例えば、導電性フィラーとして、塗料、樹脂、ゴム、ペースト、接着剤やインクなど幅広い用途に使用することができる。また、本発明のニッケル粉又はニッケル合金粉は、スポンジ状ニッケル触媒としても期待できる。 The method for producing nickel powder or nickel alloy powder in which particles having an average primary particle diameter of 50 nm or more and 1 μm or less are three-dimensionally connected according to the present invention is simple in process and the nickel salt is efficiently reduced. High yield and economical. In addition, the nickel powder or nickel alloy powder of the present invention is used in a wide range of applications such as paint, resin, rubber, paste, adhesive and ink as the conductive filler because the nanoparticles are three-dimensionally connected. can do. The nickel powder or nickel alloy powder of the present invention can also be expected as a sponge nickel catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011021250A (en) * | 2009-07-16 | 2011-02-03 | Noritake Co Ltd | Metallic material composed of metal nanoparticle, and method for producing the same |
| CN102601384A (en) * | 2012-03-31 | 2012-07-25 | 北京科技大学 | Chemical method for preparing cobalt nickel nanoscale alloy powder |
| JP2014189867A (en) * | 2013-03-28 | 2014-10-06 | Sumitomo Metal Mining Co Ltd | Method for drying nickel powder |
| CN105710384A (en) * | 2015-11-04 | 2016-06-29 | 中国科学院上海高等研究院 | One-dimensional nano bimetal alloy with hexagonal nail head structure and preparation method thereof |
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|---|---|---|---|---|
| JPS6280206A (en) * | 1985-10-02 | 1987-04-13 | Murata Mfg Co Ltd | Production of nickel powder |
| JP2007146251A (en) * | 2005-11-29 | 2007-06-14 | Sumitomo Metal Mining Co Ltd | Nickel powder, its production method and polymer-ptc element using the nickel powder |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6280206A (en) * | 1985-10-02 | 1987-04-13 | Murata Mfg Co Ltd | Production of nickel powder |
| JP2007146251A (en) * | 2005-11-29 | 2007-06-14 | Sumitomo Metal Mining Co Ltd | Nickel powder, its production method and polymer-ptc element using the nickel powder |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011021250A (en) * | 2009-07-16 | 2011-02-03 | Noritake Co Ltd | Metallic material composed of metal nanoparticle, and method for producing the same |
| CN102601384A (en) * | 2012-03-31 | 2012-07-25 | 北京科技大学 | Chemical method for preparing cobalt nickel nanoscale alloy powder |
| JP2014189867A (en) * | 2013-03-28 | 2014-10-06 | Sumitomo Metal Mining Co Ltd | Method for drying nickel powder |
| CN105710384A (en) * | 2015-11-04 | 2016-06-29 | 中国科学院上海高等研究院 | One-dimensional nano bimetal alloy with hexagonal nail head structure and preparation method thereof |
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